JP4912652B2 - Cleaning composition and method for producing the same - Google Patents

Description

The present invention is foaming power, excellent detergency relates to mild a soluble high safety detergent compositions and their preparation how the skin.

  Conventionally, alkyl benzene sulfonate, α-olefin sulfonate, alkyl sulfonic acid, and the like have been used as surfactants having excellent foaming power. Although these surfactants are excellent in foaming power, they have a degreasing power and a problem that rough skin is liable to occur. In recent years, detergents based on a less irritating polyoxyethylene alkyl ether sulfate salt as a detergent base have been dominant. However, although it has become milder to the skin, it is hard to say that it has reached a sufficiently satisfactory level.

  On the other hand, alkyl polyglycosides are known as surfactants that are excellent in foaming power even if they are nonionic surfactants (see, for example, Patent Document 1). Similarly, polyglycerol fatty acid esters are also known as surfactants that are mild to the skin and excellent in foaming power, but most of the industrially obtained products have low monoester purity and the performance of the original polyglycerol fatty acid esters. Not shown. In order to solve this problem, an attempt to increase monoester purity by adding glycidol to a fatty acid is also known (see, for example, Patent Document 2).

  However, there is always the problem that the aqueous solution of the fatty acid ester is hydrolyzed, which impairs the stability of the product. As a method for solving this problem, a monoalkyl ether of a polyol is known (see, for example, Patent Document 3). However, the production of a dialkyl ether body is unavoidable, and the industrial production of polyglycerol monoalkyl ether having a high monoether purity is unavoidable. It is hard to say that a sufficient manufacturing method has been established for the general manufacturing method.

  Further, as a detergent composition with improved liquidity, a composition in which the ratio of linear polyglycerol ether to branched polyglycerol ether is limited (see, for example, Patent Document 4), and all hydroxyl groups of polyglycerol are 1,2-diol. 1 and 3-diol (see, for example, Patent Document 5) are known, but each time the chain length of polyglycerol is extended, etherification and epoxidation are repeated. The process is complicated, and it is not satisfactory as an industrially obtained method. Because of the difficulty in adding glycerol to higher alcohols, most have a polyalkyl / alkylene oxide structure between the alkyl chain and polyglycerol (see, for example, Patent Document 4).

Patent Documents 4 and 5 show that branched polyglycerol is important for its liquidity, such as solubility in water. According to the research results of the present inventors, a polymer having a polymerization degree of 3 is shown. Although it has been confirmed that lauryl ether and lauric acid ester of linear triglycerol in glycerol have a problem in water solubility, it does not necessarily have a problem in the linear structure. It was confirmed that there was a suspicion that its water solubility was significantly affected. In addition, when the alkyl chain forms an ether bond with the terminal hydroxyl group of linear triglycerol, there is a problem with liquidity in particular, and the structure in which the hydroxyl group located at the center of the linear triglycerol is lauryl ether has a terminal lauryl ether. It has also been confirmed that its liquidity is superior to that of the product. However, a method of synthesizing such a structure by controlling the structure can be carried out by making full use of a known synthesis method, but it is not an advantageous method for industrial production, but rather a composition having a high monoalkyl ether purity. I found that the problem could be solved by getting things.
JP 58-104625 A JP-A-9-157384 JP-A-6-293688 JP-A-11-310792 JP 2001-114720 A

The present invention, detergents, i.e. mild shampoo, body shampoo, rinse, for a greater body as compared with washing the face body wash detergents such as forms, or conventional detergent compositions for use in the kitchen liquid detergent , and the detergency, foaming power, and to provide a detergent composition excellent in water solubility and its production how.

In view of the above problems, the present inventors have conducted extensive research to develop a detergent composition having high safety and excellent detergency and foaming power. As a result, the polyglycerol monohydrate represented by the general formula (1) is obtained. The above problems have been solved by using a detergent composition containing an alkyl ether, and the present invention has been made.

That is, this invention which solves the said subject has the following structure.
1. A cleaning composition containing a polyglycerol monoalkyl ether represented by the following general formula (1), wherein the column used is an ODS column by high performance liquid chromatography (HPLC) equipped with a differential refraction (RI) detector. In this case, the area ratio of the chromatogram of the detergent composition analyzed by the same apparatus is 5% or less of alkyl alcohol, 20% or less of polyglycerol, and polyglycerol monoalkyl ether represented by the following general formula (1) 75
% Detergent composition characterized by being at least%.

RO- (A) _n -H (1)
(R is an alkyl group having 1 to 24 carbon atoms, n is an average value of 2 to 20, and A is a polyglycerol having a repeating unit having a structure represented by CH ₂ CHOHCH ₂ O )

2. In the manufacturing method of the cleaning composition of said 1, the manufacturing method of the cleaning composition characterized by performing the process of the following manufacturing method 1 or the manufacturing method 2 in order.
(Manufacturing method 1)
First step: a step of reacting an alkyl alcohol and epichlorohydrin to obtain an alkyl glycidyl ether.
Second step: A step of reacting an alkyl glycidyl ether with glycerol to obtain a diglycerol monoalkyl ether.
Third step: A step of adding a glycidol to diglycerol monoalkyl ether to obtain a detergent composition containing polyglycerol monoalkyl ether represented by the general formula (1).
(Manufacturing method 2)
First step: a step of reacting an alkyl alcohol and epichlorohydrin to obtain an alkyl glycidyl ether.
Second step: a step of hydrolyzing alkyl glycidyl ether to obtain glycerol monoalkyl ether.
Third step: A step of obtaining a detergent composition containing polyglycerol monoalkyl ether represented by the general formula (1) by adding glycidol to glycerol monoalkyl ether.

According to the first aspect of the present invention, it is possible to provide a highly safe cleaning composition that is excellent in foaming power and detergency, and has low irritation to the skin.

According to invention of Claim 2, the manufacturing method of the cleaning composition which is efficient and is rich in industrial mass productivity can be provided.

  In the polyglycerol monoalkyl ether which is an active ingredient of the cleaning agent of the present invention, R represented by the general formula (1) represents a long chain aliphatic group having 1 to 24 carbon atoms, preferably 10 to 18 carbon atoms. The aliphatic group in this case includes a linear or branched alkyl group and alkenyl group. Specifically, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tridecyl, n -Tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, isopropyl, 1-methylpentyl, 1-ethylbutyl, 1-methylhexyl, 1-methylheptyl, 1- Examples include butylhexyl, 2-octenyl, 4-tetradecenyl, oleyl and the like. In addition, when the carbon number of R is 26 or more, the effect of the present invention cannot be obtained.

  In the general formula (1), n is an average degree of polymerization of glycerol, preferably 2 to 20, and more preferably 4 to 20. In addition, when the average degree of polymerization of n exceeds 20, the effect of the present invention cannot be obtained.

In the polyglycerol monoalkyl ether which is an active ingredient of the cleaning composition of the present invention, the analysis values of unreacted alkyl alcohol, polyglycerol monoalkyl ether and by-produced polyglycerol are 5% or less, 75% or more and 20%, respectively. It is preferable to be in the following range. Alkyl unreacted alcohol exceeds 5%, the lack of a water-soluble, even less than 5%, the polyglycerol by-produced is more than 20%, the active ingredients of no problem in water-soluble but detergent composition Since it decreases, the foaming power and the cleaning power are impaired, which is not preferable. In addition to polyglycerol monoalkyl ethers, dialkyl ethers, trialkyl ethers, and other polyglycerol polyalkyl ethers with a dialkyl ether or higher content exceeding 5% impair foaming power and detergency, and satisfy the desired performance. Since a large amount of blending is required, it is set to 5% or less .

An example of analysis by HPLC is shown in FIG.
These analyzes can be performed using an aqueous methanol solution as an eluent in an HPLC analyzer equipped with an RI detector and an ODS column. Specifically, in the chromatogram obtained from the HPLC analyzer, the free polyglycerol (A), the polyglycerol monoalkyl ether portion (B), and the free alcohol portion (C) refer to the portions shown in FIG.

  The apparatus used for the measurement was HPLC (LC-10ADVP pump, CTO-10ACVP column oven, SIL-10ADVP autosampler, RID-10A differential refraction detector, CLASS-VP analysis software) manufactured by Shimadzu Corporation, and the column was an ODS column (Shim). -Pack CLC-ODS (M)) In the moving bed, 90% aqueous methanol solution was 1.0 ml / min, and the column temperature was 40 ° C.

  The polyglycerol monoalkyl ether according to the present invention comprises an alkyl alcohol and 3 to 5 equivalents of glycidol reacted at 50 to 100 ° C. under an alkali catalyst and unreacted alkyl alcohol at 130 to 200 ° C. under reduced pressure. And by a known method for distilling off free polyglycerol.

  As an efficient industrial method for producing the polyglycerol monoalkyl ether according to the present invention, the present inventors have devised a method of reacting glycidol with diglycerol monoalkyl ether or glycerol monoalkyl ether. explain.

  The method of adding glycidol to diglycerol alkyl ether includes the first step of obtaining alkyl glycidyl ether, the second step of reacting alkyl glycidyl ether and glycerol to obtain diglycerol monoalkyl ether, and adding glycidol to diglycerol monoalkyl ether. It consists of a third step to be added.

  The method of adding glycidol to glycerol alkyl ether includes the first step of obtaining alkyl glycidyl ether, and dissolving alkyl glycidyl ether in an aprotic solvent, followed by hydrolysis using an acid catalyst such as dilute sulfuric acid, It consists of a second step of obtaining glycerol monoalkyl ether and a third step of adding glycidol to glycerol monoalkyl ether.

[Production from diglycerol monoalkyl ether]
1 mol of epichlorohydrin is dissolved in 1 mol of alkyl alcohol in an organic solvent such as toluene, and reacted at 30 ° C. to 50 ° C. for several hours using an aqueous sodium hydroxide solution and tetrabutylammonium iodine as a phase transfer catalyst. After completion of the reaction, the aqueous layer is separated, and the organic layer is washed with a saturated aqueous ammonium chloride solution, dried over anhydrous sodium sulfate, and the solvent is distilled off to obtain a crude alkyl glycidyl ether. After distilling off unreacted alcohol and the like by distillation under reduced pressure, the alkyl glycidyl ether is distilled and purified.

  Subsequently, 3-5 times equivalent of glycerin is added to 1 mol of this alkyl glycidyl ether, and ring-opening reaction is carried out at 200 ° C. to 250 ° C. under an alkali catalyst to obtain a crude diglycerol monoalkyl ether. Crude diglycerol monoalkyl ether is purified by distilling off unreacted alkyl glycidyl ether, glycerol and the like by distillation under reduced pressure, and then distilling diglycerol monoalkyl ether.

  This purified diglycerol monoalkyl ether does not contain any dialkyl ether or trialkyl ether other than the monoalkyl ether. Further, depending on the length of the alkyl chain, it can be further purified by recrystallization from methanol or ethyl acetate.

  Glycidol is added at 1 to 18 times equivalent glycidol in an inert gas atmosphere at a reaction temperature of 100 ° C. to 150 ° C. using an alkali catalyst depending on the target average degree of polymerization per mole of the purified diglycerol monoalkyl ether. Glicidol is added at a rate of about 1 ml / min with stirring. After completion of the dropwise addition, stirring is continued for several hours to obtain polyglycerol monoalkyl ether. If necessary, the alkali used in the catalyst is neutralized with phosphoric acid or the like.

  The polyglycerol monoalkyl ether obtained in this way is a polyglycerol monoalkyl ether having a polymerization degree of 2 or more, not including a polymerization degree of glycerol, and having no polyether such as dialkyl ether or trialkyl ether. It is.

[Production from glycerol monoalkyl ether]
The alkyl glycidyl ether obtained above is dissolved in a solvent such as dioxane, diluted sulfuric acid is added, and the mixture is refluxed at 90 ° C. for 1 hour. After neutralizing sulfuric acid with an equivalent amount of sodium carbonate, dioxane and water were distilled off, and further dissolved in ethyl acetate, washed with saturated ammonium chloride, dried over anhydrous sodium sulfate, and then ethyl acetate was distilled off. A highly pure glycerol monoalkyl ether can be obtained.

  Depending on the alkyl chain length, a highly purified glycerol monoalkyl ether can be obtained by recrystallization from ethyl acetate. Sodium hydroxide was used as a catalyst in the obtained glycerol monoalkyl ether, and 1 to 19 times equivalent glycidol was added dropwise at about 1 ml / min depending on the desired average degree of polymerization at 100 ° C. to 120 ° C. in an inert gas atmosphere. Append. Stirring is continued for several hours after the dropwise addition to obtain polyglycerol monoalkyl ether. Sodium hydroxide used for the catalyst is neutralized with an equivalent amount of phosphoric acid.

  The polyglycerol monoalkyl ether thus obtained does not contain dialkyl ether, trialkyl ether, etc., and is a reaction product between polyglycerol monoalkyl ether of a more complicated polymer having a polymerization degree of 1 and glycidol. It consists of polyglycerol, a by-product that is not bound to alkyl alcohol.

[Purification of polyglycerol monoalkyl ether]
The polyglycerol monoalkyl ether thus obtained contains polyglycerol which is a polymer of a polyglycerol monoalkyl ether having a polymerization degree of 1 or more or a polymerization degree of 2 or more and glycidol, depending on the starting material. The polyglycerol monoalkyl ether having a polymerization degree can be removed by using a technique such as vacuum distillation, molecular distillation, solvent extraction, or chromatography after completion of the reaction. Industrially superior methods include removal by vacuum distillation, preferably molecular distillation.

  In the present invention, the area ratio in the analysis method described above is such that the remaining amount of unreacted alkyl alcohol is 5% or less, whereby a composition having excellent water solubility can be obtained. Since glycidol is added to monoalkyl ether or diglycerol monoalkyl ether, a composition with a very low content of unreacted alkyl alcohol can be obtained. Furthermore, by removing those having a low polymerization degree, such as diglycerol monoalkyl ether and glycerol monoalkyl ether, by molecular distillation or the like to 15% or less and 10% or less, respectively, a more excellent water-soluble composition can be obtained. .

The average degree of polymerization of polyglycerol fatty acid ester or polyglycerol monoalkyl ether can be calculated using the following formula 2 based on the hydroxyl value. However, although the detergent composition according to the present invention is characterized in that the content of polyglycerol by glycidol is small, the inclusion of polyglycerol still greatly increases the average degree of polymerization obtained from Equation 2.

  Therefore, the effective addition mole number of glycidol calculated from Equation 3 was used as the average degree of polymerization in the present invention. Specifically, the polyglycerol content is obtained from the HPLC analysis result, and the amount of glycidol added to the molecule containing the alkyl chain is calculated from the glycidol used in the reaction. The value obtained by dividing by the number of moles of alkyl ether, diglycerol monoalkyl ether, and alkyl alcohol was defined as the effective number of moles added. When glycerol monoalkyl ether was used as a starting material, 1 was added to this effective addition mole number, and when diglycerol monoalkyl ether was used as a starting material, 2 was added to this effective addition mole number. Specifically, the average degree of polymerization was calculated using the following formula 3.

  The degree of polyglycerol polymerization of the polyglycerol monoalkyl ether thus obtained is preferably up to 20, and when the degree of polymerization is higher than this, the dominance of the hydrophilic group portion in the molecule increases, and the foaming power and detergency are reduced. To do. In addition, the viscosity becomes remarkably high and handling becomes difficult.

n: Average degree of polymerization OHV: Hydroxyl value [mgKOH / ml]
MW _al: average molecular weight of alkyl alcohol

n: Average polymerization degree (number of added moles)
n _S : Number of glycerol added to the raw material in advance
If starting from glycerol alkyl ether, if starting from 1, diglycerol
2. 0 from alkyl alcohol
a _A : area ratio of polyglycerol moiety (A) in HPLC analysis result a _C : area ratio of alkyl alcohol moiety (C) in HPLC analysis result W _A ; amount of alcohol containing alkyl chain [g]
W _G ; amount of glycidol used [g]
W _R : amount of glycidol and alkyl alcohol used in the reaction [g]
C _d : Cut rate by distillation MW: Molecular weight of alkyl chain (as alcohol)

The wash cleaning agent composition of the present invention is a skin, hair cleanser, facial cleansers, shampoos, rinses, body shampoos, soaps also, oral cleaning agents, such as toothpaste and mouthwash, solid, paste And cleaning compositions used for liquid clothing cleaning agents and the like . In addition, various detergent compositions used for industrial use can be mentioned .

The engagement Ru wash cleaning agent composition in the present invention by a combination of interfacial active agent, can be used as a detergent composition was in various applications set forth above. The surfactants that can be used together are shown below, but are not particularly limited thereto.

Anionic surfactants Anionic surfactants include alkyl sulfates, polyoxyethylene alkyl sulfates, α-sulfo fatty acid ester salts, α-olefin sulfonates, alkyl or hydroxyalkyl ether carboxylates, N-acyls. Taurine, N-acylated methyltaurine, N-acylated glucin, N-acylated aspartic acid, N-acylated sarcosine, N-acylated glutamic acid, monoalkyl phosphate ester salt, alkylamide ether sulfate ester, fatty acid monoglyceride Sulfate, alkyl glyceryl ether sulfate, alkyl polyglyceryl ether sulfate, alkyl iminodicarboxylate, secondary amide type N-acyl amino acid salt, tartaric acid alkylamide, malic acid alkylamide Citric acid alkyl amides.

Cationic surfactants Examples of cationic surfactants include mono- or dialkyl quaternary ammonium salts, mono- or dialkyl quaternary ammonium salts having an ether group or an ester group, or hydrochlorides, sulfates, organic acid salts thereof, and the like. .

Amphoteric surfactants Amphoteric surfactants include amide amino acid type amphoteric surfactants, long-chain alkyldimethylcarboxymethylbetaine, sulfobetaine, amidopropylbetaine, imidazolium betaine, glycine type, and alanine type amphoteric surfactants. Agents, carboxybetaines, sulfobetaines, phosphobetaines, amide amino acids, imidazolinium betaine surfactants, and the like.

Nonionic surfactants Nonionic surfactants include alkyl polyhydric alcohol ethers, hydroxyalkyl polyhydric alcohol ethers, higher alcohol ethoxylates, higher alcohol ethoxypropoxylates, nonylphenol ethoxylates, fatty acid alkanolamides, and sucrose. Fatty acid ester, alkyl (poly) glycoside, sorbitan fatty acid ester, glycerol fatty acid ester, polyglycerol fatty acid ester, fatty acid 2,3-dihydroxypropylamide, fatty acid polyoxyethyleneamide, alkylamine oxide, alkylamidoamine oxide, polyoxyethylene fatty acid ester Methyl or ethyl glycoside, fatty acid ester, acyl glucamide and the like.

  Moreover, the auxiliary | assistant component mix | blended with a cleaning agent can be mix | blended with the cleaning composition of this invention as needed. Such auxiliary components include builders, moisturizers, viscosity modifiers, antiseptics, anti-inflammatory agents, antioxidants, UV absorbers, sequestering agents, migration inhibitors, antibacterial agents, and water-soluble polymer compounds. , Water-soluble inorganic salts, pH adjusters, pearl brighteners, dyes, fragrances, enzymes, bleaching agents and the like. In particular, when used as a hard surface cleaner for business use, industrial use, automatic dishwashers, etc., it is preferable to use it under alkaline conditions containing an alkali agent. It can be used in alkali and acidic pH ranges, which is not possible with glycerol fatty acid SELL.

[Example 1]
Examples of the present invention and comparative examples are shown below to specifically explain the present invention. As a test method, a detergency test, a foaming test, and an irritation were performed and compared. The results are shown in Table 1.

Evaluation criteria and detergency test The nutnut detergency test described in JIS-K3370 was followed. The removal rate of dirt was obtained from the difference in weight between the amount of slide glass adhering and the remaining amount after washing. The cleaning water was 30 ° C. tap water, and the cleaning composition concentration was 0.05% by mass and 0.10% by mass.

・ Foamability test In accordance with the method described in JIS-K3362, a 0.1% by weight and 0.2% by weight sample aqueous solution was dropped under the conditions of 25 ° C. and 40 ° C. using a Ross Miles foam tester. The foamability was evaluated based on the height of the generated foam. Tap water was used as dilution water.

Evaluation is based on the following four-step method.
◎ 250 mm or more ○ 200 mm or more, less than 250 △ 150 mm or more, less than 200 × less than 150 mm

・ Irritation Irritation to the skin was examined by a patch test (occlusion patch test method).

  A diluted solution containing 0.5% by mass of the product of the present invention and the comparative product is prepared. Distilled water 89.5% by mass, ethanol 10.0% by mass, invention or comparative product 0.5% by mass. This diluted solution is soaked in a circular filter paper having a diameter of about 5 mm, and this is attached to the upper arm. The sticking method is to cover the filter paper with an aluminum disk (fin chamber) of the same diameter and fix it with tape. After sticking for 48 hours, the filter paper is peeled off (patch removal), and after that, the skin is stimulated and reacted after 24 hours.

Evaluation is based on the following five-step method.
No reaction: -0
Very light erythema: ± 0.5
Erythema: +1.0
Erythema and edema: ++ 2.0
Erythema, edema and blisters: +++ 3.0

  Five levels, each coefficient is set to 0, 0.5, 1.0, 2.0, and 3.0, respectively, and the sum of the number of responding persons multiplied by the coefficient is used as a score. The score obtained by dividing the score by 1 person (48 hours determination) and 24 hours (72 hours determination) after dividing the patch by the number of subjects is 100 times. A stimulation index of less than 10 was evaluated as ◯, 10-30 as △, and more than 30 as ×. The test was performed by 20 people.

Water solubility test To confirm water solubility, the turbidity of a 5% aqueous solution of each of the product of the present invention and the comparative product was measured using a turbidimeter NDH2000 from Nippon Denshoku Industries Co., Ltd. The turbidity was less than 0.1, and 0.1 or more was rated as x.

[Production example]
<Invention 1>
Sodium hydroxide (5.746 g, 0.144 mol) was used as a catalyst for 175 g (0.9392 mol) of lauryl alcohol and 212.8 g (2.873 mol) of glycidol. In the reaction, lauryl alcohol and sodium hydroxide were reacted to form an alkoxide, 200 ml of toluene was added, and glycidol was added dropwise at a reaction temperature of 90 ° C. at a rate of about 0.8 ml / min. After completion of the dropwise addition, the mixture was further aged at 90 ° C. for 6 hours. The reaction was carried out in an inert gas atmosphere.

  After completion of the reaction, the catalyst was neutralized with an equivalent amount of phosphoric acid, the polyglycerol separated from the neutralized salt was filtered off, and toluene was distilled off to obtain 390 g of polyglycerol monolauryl ether. Furthermore, unreacted lauryl alcohol was distilled off by distillation under reduced pressure (0.92 kPa, 150 to 180 ° C., charge 15.3% cut). Analysis values of 330 g of the obtained polyglycerol monolauryl ether were 0.2%, 95.3%, and 4.5% for lauryl alcohol, polyglycerol monolauryl ether, and polyglycerol, respectively. Each component was analyzed by the HPLC method. The average degree of polymerization calculated from Equation 3 was 4.3.

  The hydroxyl value of the resulting polyglycerol monolauryl ether was 609.0 mgKOH / ml, and the polyglycerol part not introduced with an alkyl chain, which is a polymer of glycidol, was virtually determined from the hydroxyl value as a monoalkyl ether. The average degree of polymerization was 5.2.

<Invention 2>
186.3 g (0.9998 mol) of lauryl alcohol and 138.8 g (1.500 mol) of epichlorohydrin are dissolved in 300 ml of toluene, and 240 ml of 30% NaOH and 3.694 g (0.010 mol) of tetrabutylammonium iodine are used as a phase transfer catalyst. The reaction was vigorously stirred at 40 ° C. for 5 hours. After completion of the reaction, the aqueous layer was separated, and the organic layer was washed with a saturated aqueous ammonium chloride solution and dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain crude lauryl glycidyl ether. This was purified by distillation under reduced pressure (0.21 kPa, 160 to 180 ° C.). The obtained lauryl glycidyl ether was 185 g (yield: 76.3%). The purity was 97.3% by area ratio according to GPC analysis using THF as an eluent.

  The obtained lauryl glycidyl ether 150.0 g (0.6188 mol) and glycerol 170.8 g (1.8547 mol) were heated to 220 ° C. in an inert gas atmosphere using 1.600 g of sodium hydroxide as a catalyst, Monolauryl ether was obtained. After neutralizing sodium hydroxide used as a catalyst with an equivalent amount of phosphoric acid, the neutralized salt was filtered off, unreacted glycerol was distilled off, and diglycerol monolauryl ether was distilled (0.26 kPa, 240 ° C.) As a result, diglycerol monolauryl ether having a purity of 98.0% was obtained in a yield of 87.9%.

  To 180 g (0.511 mol) of the obtained diglycerol monolauryl ether, 0.422 g of sodium hydroxide catalyst was used, and 205 g (2.7673 mol) of glycidol was added at a reaction temperature of 120 ° C. in an inert gas atmosphere. Glycidol was added at a rate of about 1 ml / min with stirring. The dropping was completed in about 3 and a half hours, and stirring was continued for another 6 hours to obtain polyglycerol monolauryl ether. Sodium hydroxide used for the catalyst was neutralized with an equivalent amount of phosphoric acid. Each component was analyzed by the HPLC method. Lauryl alcohol, polyglycerol monolauryl ether, and polyglycerol were 0.0%, 91.5%, and 8.5%, respectively. The average degree of polymerization obtained from Formula 3 was 4.4. The hydroxyl value was 680.1 mgKOH / ml, and the average degree of polymerization of polyglycerol monolauryl ether obtained from Formula 2 was 6.5.

<Invention 3>
30.1 g (0.124 mol) of lauryl glycidyl ether having a purity of 98.3% obtained in the same manner as invented product 2 was dissolved in 60 g of dioxane, and 15 g of 5% H ₂ SO ₄ was added. Reflux for hours. After neutralizing sulfuric acid with an equivalent amount of sodium carbonate, dioxane and water were distilled off, and further dissolved in ethyl acetate, washed with saturated ammonium chloride, dried over anhydrous sodium sulfate, ethyl acetate was distilled off, and purity 99 .3% glycerol monolauryl ether was obtained in 95.0% yield.

  To 30.0 g (0.115 mol) of the obtained glycerol monolauryl ether, 34.1 g (0.461 mol) of glycidol was added dropwise at 1 ml / min at 120 ° C. in an inert gas atmosphere using 0.128 g of sodium hydroxide as a catalyst. Added. Stirring was continued for 6 hours after the dropwise addition to obtain polyglycerol monolauryl ether. Sodium hydroxide used for the catalyst was neutralized with an equivalent amount of phosphoric acid. Each component was analyzed by the HPLC method. Lauryl alcohol, polyglycerol monolauryl ether, and polyglycerol were 0.0%, 90.7%, and 9.3%, respectively. The average degree of polymerization obtained from Formula 3 was 4.1. The hydroxyl value was 628.0 mgKOH / ml, and the average degree of polymerization of polyglycerol monolauryl ether obtained from the formula 2 was 6.5.

<Invention 4>
200.0 g (1.264 mol) of decanyl alcohol and 175.4 g (1.895 mol) of epichlorohydrin were dissolved in 300 ml of toluene / hexane (1/1), 240 ml of 30% NaOH aqueous solution and 3.694 g (0,4) of tetrabutylammonium iodine. The reaction was vigorously stirred at 40 ° C. for 5 hours using .010 mol) as the phase transfer catalyst. After completion of the reaction, the aqueous layer was separated, and the organic layer was washed with a saturated aqueous ammonium chloride solution and dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain crude decanyl glycidyl ether. This was purified by vacuum distillation (0.21 kPa, 150-170 ° C.). The obtained decanyl glycidyl ether was 198.3 g (yield 73.2%). The purity was 98.2% as an area ratio by GPC analysis using THF as an eluent.

100 g (0.4667 mol) of obtained decanyl glycidyl ether was dissolved in 200 g of dioxane, 30 g of 5% H ₂ SO ₄ was added, and the mixture was refluxed at 90 ° C. for 1 hour. After neutralizing sulfuric acid with an equivalent amount of sodium carbonate, dioxane and water were distilled off, and further dissolved in ethyl acetate, washed with saturated ammonium chloride, dried over anhydrous sodium sulfate, ethyl acetate was distilled off, and purity 99 8% glycerol monodecanyl ether was obtained in 96.4% yield. To 100.0 g (0.430 mol) of the obtained glycerol monodecanyl ether, 0.430 g of sodium hydroxide was used as a catalyst, and 127.53 g (1.722 mol) of glycidol was added dropwise at 1 ml / min in an inert gas atmosphere at 120 ° C. Added. Stirring was continued for 6 hours after the dropwise addition to obtain polyglycerol monodecanyl ether. Sodium hydroxide used for the catalyst was neutralized with an equivalent amount of phosphoric acid. Each component was analyzed by the HPLC method. Decanyl alcohol, polyglycerol monodecanyl ether, and polyglycerol were 0.0%, 93.8%, and 6.2%, respectively. The average degree of polymerization obtained from Formula 3 was 4.2. The hydroxyl value was 648.7 mgKOH / ml, and the average degree of polymerization of polyglycerol monolauryl ether obtained from the formula 2 was 5.8.

<Invention 5>
Stearyl alcohol 200.0 g (0.7394 mol) and epichlorohydrin 102.6 g (1.109 mol) were dissolved in 500 ml of toluene / hexane (1/1), 240 ml of 30% NaOH aqueous solution and 3.694 g (0.34 g) of tetrabutylammonium iodine. The reaction was vigorously stirred at 60 ° C. for 5 hours using 010 mol) as the phase transfer catalyst. After completion of the reaction, the aqueous layer was separated, and the organic layer was washed with a saturated aqueous ammonium chloride solution and dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain crude stearyl glycidyl ether. This was purified by vacuum distillation (0.21 kPa, 190-210 ° C.). The obtained stearyl glycidyl ether was 158.9 g (yield 65.8.%). The purity was 99.6% by area ratio according to GPC analysis using THF as an eluent.

120 g (0.367 mol) of the obtained stearyl glycidyl ether was dissolved in 200 g of dioxane, 30 g of 5% H ₂ SO ₄ was added, and the mixture was refluxed at 90 ° C. for 1 hour. After neutralizing sulfuric acid with an equivalent amount of sodium carbonate, dioxane and water were distilled off, further dissolved in ethyl acetate, washed with saturated ammonium chloride, dried over anhydrous sodium sulfate, and then recrystallized from ethyl acetate to a purity of 99. 114.1 g (yield 90.2%) of 8% glycerol stearyl ether was obtained. To 100.0 g (0.290 mol) of the obtained glycerol monostearyl ether, 451.5 g (6.095 mol) of glycidol was added dropwise at 1 ml / min at 120 ° C. in an inert gas atmosphere using 0.455 g of sodium hydroxide as a catalyst. Added. Stirring was continued for 6 hours after the dropwise addition to obtain polyglycerol monostearyl ether. Sodium hydroxide used for the catalyst was neutralized with an equivalent amount of phosphoric acid. Each component was analyzed by the HPLC method. Stearyl alcohol, polyglycerol monostearyl ether, and polyglycerol were 0.0%, 90.8%, and 9.2%, respectively. The average degree of polymerization obtained from Formula 3 was 19.3. The hydroxyl value was 684.5 mgKOH / ml, and the average degree of polymerization of polyglycerol monolauryl ether obtained from the formula 2 was 23.9.

<Comparison product 1>
Glycidol at a reaction temperature of 140 ° C. under an inert gas atmosphere using 173.8 g (0.9327 mol) of lauryl alcohol, 226.2 g (3.054 mol) of glycidol and 4.886 g (0.1222 mol) of sodium hydroxide as a catalyst. Was added dropwise at a rate of 1 ml / min. After completion of the reaction, the catalyst was neutralized with phosphoric acid and filtered off. Unreacted lauryl alcohol was distilled off under reduced pressure (0.73 kPa, 150 to 180 ° C., 30% cut against charging). The obtained polyglycerol monolauryl ether 302 g was analyzed by the HPLC method. Lauryl alcohol, polyglycerol monolauryl ether, and polyglycerol were 0.4%, 62.7%, and 36.9%, respectively. The average degree of polymerization calculated | required from Formula 3 of the obtained composition polyglycerol monolauryl ether was 23.9. The hydroxyl value was 755.0 mgKOH / ml, and the average degree of polymerization of polyglycerol monolauryl ether obtained from Formula 2 was 467.9.

  The average degree of polymerization determined from the hydroxyl value of Comparative Product 1 is higher than that of the other products because the content of polyglycerol not ether-bonded is high.

<Comparison product 2>
Using 256.3 g (1.376 mol) of lauryl alcohol, 378.1 g (5.104 mol) of glycidol and 6.720 g (0.168 mol) of sodium hydroxide as a catalyst, the reaction temperature was 90 ° C., and glycidol was 0.2 ml / min. Added dropwise at a rate. The reaction was performed under an inert gas atmosphere. After completion of the reaction, the catalyst was neutralized with phosphoric acid, and the neutralized salt was filtered off to obtain 632.1 g of polyglycerol monolauryl ether. Further, unreacted lauryl alcohol was distilled off by distillation under reduced pressure (0.56 kPa, 150 to 180 ° C., cut to 8% for charging). Analysis values of 581.2 g of the obtained polyglycerol monolauryl ether were 6.8%, 84.4%, and 8.8% for lauryl alcohol, polyglycerol monolauryl ether, and polyglycerol, respectively. Each component was analyzed by the HPLC method. The average degree of polymerization obtained from Formula 3 was 3.0. The hydroxyl value was 587.5 mgKOH / ml, and the average degree of polymerization of polyglycerol monolauryl ether obtained from the formula 2 was 4.2.

Furthermore, as comparative products, Poem J-0021 manufactured by Riken Vitamin Co., Ltd., M-12J manufactured by Taiyo Kagaku Co., Ltd., and Polypropylene Monolaurate Comparative Product 5 manufactured by Nikko Chemicals Co., Ltd. For SBL-3N-27 and laureth-3-sodium sulfate comparative product 6, SLS sodium lauryl sulfate manufactured by Nikko Chemicals was used.

[Example 2]
The excellent foaming power of the invention was compared with existing foaming agents. Formulation based on amine soap using coconut oil diethanolamide (CDE) and coconut oil-N-carboxy-N-hydroxyalkylimidazolinium betaine (CPB), which are generally used as foaming agents as comparative products Comparison of foaming power by the Ross-Miles method was performed. The body soap was prepared by dissolving 400 g of triethanolamine in 1 L of warm water and heating to 75 ° C. Next, a mixed melt of 160 g of oleic acid, 160 g of lauric acid and 80 g of myristic acid was added to prepare an aqueous amine soap solution. Furthermore, 100 g of the product of the present invention or the above-mentioned foam increasing agent was added, mixed and stirred, and cooled to form a body soap. The foaming power test by the Ross Miles method was performed at water temperatures of 25 ° C. and 40 ° C., body soap concentrations of 0.1% and 0.2%. The results are shown in Table 2. Evaluation criteria are the same as in Example 1.

  A detergent composition having low irritation to the human body and excellent foaming power and cleaning power can be obtained.

Graph showing an example of high performance liquid chromatography (HPLC) analysis equipped with a differential refraction (RI) detector

Claims (2)

A cleaning composition containing a polyglycerol monoalkyl ether represented by the following general formula (1), wherein the column used is an ODS column by high performance liquid chromatography (HPLC) equipped with a differential refraction (RI) detector. In this case, the area ratio of the chromatogram of the detergent composition analyzed by the same apparatus is 5% or less of alkyl alcohol, 20% or less of polyglycerol, and polyglycerol monoalkyl ether represented by the following general formula (1) Is a cleaning composition characterized by being 75% or more.
RO- (A) _n -H (1)
(R is an alkyl group having 1 to 24 carbon atoms, n is an average value of 2 to 20, and A is a polyglycerol having a repeating unit having a structure represented by CH ₂ CHOHCH ₂ O)
The manufacturing method of the cleaning composition of Claim 1 WHEREIN: The manufacturing method of the cleaning composition characterized by performing the process of the following manufacturing method 1 or the manufacturing method 2 in order.
(Manufacturing method 1)
First step: a step of reacting an alkyl alcohol and epichlorohydrin to obtain an alkyl glycidyl ether.
Second step: A step of reacting an alkyl glycidyl ether with glycerol to obtain a diglycerol monoalkyl ether.
Third step: A step of adding a glycidol to diglycerol monoalkyl ether to obtain a detergent composition containing polyglycerol monoalkyl ether represented by the general formula (1).
(Manufacturing method 2)
First step: a step of reacting an alkyl alcohol and epichlorohydrin to obtain an alkyl glycidyl ether.
Second step: a step of hydrolyzing alkyl glycidyl ether to obtain glycerol monoalkyl ether.
Third step: A step of obtaining a detergent composition containing polyglycerol monoalkyl ether represented by the general formula (1) by adding glycidol to glycerol monoalkyl ether.

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